Fluorotriazine containing naphthylazonaphthyl monoazo reactive dyes

ABSTRACT

Reactive dyestuffs which, in the form of the free acid, have the following formula ##STR1## in which the substituents have the meaning given in the description, are suitable for the dyeing and printing of hydroxyl- and amido-containing materials, in particular cellulose materials.

This application is a continuation of application Ser. No. 08/019,751, filed on Feb. 18, 1993, now abandoned.

The present invention relates to new reactive dyestuffs, a process for their preparation and their use.

Reactive dyestuffs which contain, as the chromophore, an azo compound based on naphthalenesulphonic acid have already been disclosed in EP 299,315 (=U.S. Pat. No. 4,988,803).

The present invention relates to reactive dyestuffs which, in the form of the free acid, have the following formula ##STR2## in which R is hydrogen or sulpho,

A is a substituted or unsubstituted amino group, in particular one of the formula ##STR3## in which R¹ represents hydrogen or an aliphatic, cycloaliphatic or araliphatic radical and

R² represents R¹ or a heteroaryl radical or an aromatic radical, it being possible for the radicals R¹ and R² with or without inclusion of a heteroatom to form a ring.

Further heteroatoms for the ring formation of R² and R¹ are preferably O, NH, NCH₃, NCOCH₃, N--C₂ H₄ SO₂ CH═CH₂, S,SO,SO₂.

Preferred heteroaryl radicals R² and R¹ are 3-aminosulpholane, 2-aminothiazole, 6-amino-2-ethylsulphonyl- benzothiazole.

In a preferred embodiment, --NR¹ R² represents the radical of an aliphatic amine or of a heterocyclic amine in which R¹ and R² together with the joint N atom form a ring.

The aliphatic radicals represented by R¹ and R² are preferably alkyl radicals, in particular those having 1 to 6 C atoms, which may be interrupted by heteroatoms and are substituted or unsubstituted.

Examples of interrupting heteroatoms are:

O, S, SO₂, (is hydrogen, C₁ -C₄ -alkyl), NR³ CO, NR³ SO₂ ;

Examples of substituents are:

OH, Cl, F, COOH, SO₃ H, OSO₃ H, SO₂ CH═CH₂, CN, SO₂ CH₂ CH₂ Cl, SO₂ CH₂ CH₂ OSO₃ H,NR³ --Z,

in which Z represents a heterocyclic reactive group, in particular one from the monochloro- and monofluorotriazine series or fluoropyrimidine series.

The cycloaliphatic radicals R¹ are in particular 5- or 6-membered cycloalkyl radicals.

The araliphatic radicals R¹ are in particular those of the formula ##STR4## in which n is 1 to 4 and the radical A can be substituted, for example by Cl, NO₂, COOH, SO₃ H, CH₃, OCH₃, SO₂ CH₂ CH₂ OSO₃ H, SO₂ CH═CH₂, CH₂ SO₂ CH₂ CH₂ OSO₃ H.

Aromatic radicals R² are in particular phenyl or naphthyl radicals which are unsubstituted or substituted, in particular by OCH₃, OC₂ H₅, OCH₂ CH₂ OH, CH₃, C₂ H₅, --CH(CH₃)₂, F, Cl, Br, COOH, SO₃ H, NO₂, SO₂ CH₂ CH₂ OSO₃ H, SO₂ CH═CH₂, CH₂ SO₂ CH₂ CH₂ SO₃ H, CH₂ SO₂ CH═CH₂, NHZ, Z having the above-mentioned meaning.

Individual examples of R¹ or R² aliphatic radical are as follows:

CH₃, C₂ H₅, CH₂ CH₂ OH, CH₂ CH₂ OCH₃, CH₂ CH₂ OCH₂ OC₂ H₅, CH₂ CH₂ OCH₂ CH₂ OH, CH₂ SO₃ H, CH₂ CH₂ SO₃ H, CH₂ CH₂ OSO₃ H, CH₂ COOH, CH₂ CH₂ COOH, CH₂ CH₂ SO₂ CH₂ CH₂ OSO₃ H, CH₂ CH₂ OCH₂ CH₂ SO₂ CH₂ CH_(Cl), CH₂ CH₂ CH₂ CH₂ SO₂ CH═CH₂, CH₂ CH₂ NHCOCH₂ CH₂ COOH, CH₂ CH₂ CH₂ SO₂ CH₂ CH₂ SO₃ H, CH₂ CH₂ CH₂ SO₂ CH═CH₂, CH₂ CH₂ CH₂ SO₂ CH₂ CH₂ Cl, ##STR5##

Examples of cycloaliphatic radicals R¹ and R² are: ##STR6## Examples of araliphatic radicals R¹ are:

Examples of aromatic radicals R² are as follows: ##STR7##

Examples or ring-closed radicals are: ##STR8## are ##STR9##

Preferred compounds in the context of the formula (1) are those in which R represents hydrogen. Further preference is given to those compounds in which R¹ and R², independently of one another, denote hydrogen, C₁ -C₄ -alkyl, which can be substituted by OCH₃, OC₂ H₅, COOH, OSO₃ H, SO₃ H, OCH₂ CH₂ SO₂ CH₂ OSO₃ H, OCH₂ CH₂ SO₂ CH═CH₂, OCH₂ CH₂ SO₂ CH₂ CH₂ Cl, SO₂ CH₂ CH₂ OSO₃ H, SO₂ CH═CH₂ ; in a further preferred embodiment, R¹ denotes hydrogen or C₁ --C₄ -alkyl and R² denotes a phenyl radical, which can be substituted by Cl, OCH₃, CH₃, SO₃ H, NO₂, COOH, CN, SO₂ CH₂ CH₂ OSO₃ H, SO₂ CH═CH₂, CH₂ SO₂ CH₂ CH₂ OSO₃ H, CH₂ SO₂ CH═CH₂.

In a further preferred embodiment, A represents the radical of a ring-closed amine, in particular ##STR10## The invention furthermore relates to a process for the preparation of the dyestuffs of the formula (1), which is characterised in that first 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid is condensed with trifluorotriazine in a pH range from 2 to 6, in particular 3 to 5, and at temperatures of -5° to +20°, in particular at 0° to 5°, if appropriate in the presence of a buffer, to give a difluorotriazine compound, and subsequently a further fluorine atom is exchanged for an amine radical A and finally the resulting monofluoro compound is coupled with the diazo compound of an amine of the formula ##STR11## in a neutral range.

Suitable buffers are in particular the alkali metal salts of the fluorides or phosphates.

The reactive dyestuffs of the formula (1) can be isolated and processed to give useful, dry dyestuff preparations. Isolation preferably takes place at the lowest possible temperatures by salting out and filtration. The filtered dyestuffs can be dried, if appropriate by addition of a buffer mixture, for example mono- and disodiumphosphate; preferably, drying takes place at temperatures which are not excessively high and under reduced pressure. In certain cases, the dry preparations according to the invention can be prepared directly, i.e. without intermediate isolation of the dyestuffs, by spray-drying the entire preparation mixture.

The new dyestuffs are suitable for the dyeing and printing of hydroxyl- and amido-containing materials, in particular cellulose materials. They are distinguished by high reactivity and a high degree of fixation. The dyeings or prints on cellulose materials obtainable using these dyestuffs are moreover distinguished by a high stability of their fibre to dyestuff bond and by excellent stability to oxidising agents, such as peroxide- or chlorine-containing detergents. The ability of the hydrolysis products formed only to a small extent during dyeing or printing to be washed out is excellent. The dyestuffs have good wet fastness properties.

The formulae given are those of the free acids. During the preparation, the salts are in general obtained, in particular the alkali metal salts, such as sodium salts, potassium salts or lithium salts.

The weights given in the examples are those of the free acid. The colour indicator numbers given in the examples refer to the Colour Index Hue Indication Chart (Indicator Numbers).

EXAMPLE 1

31.9 g of 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid are dissolved in 400 ml of water under neutral conditions. 300 g of ice are then added, and 8.8 ml of trifluorotriazine are run in while maintaining a pH of 4.0 to 4.5 with 15% strength sodium carbonate solution. A sample is taken in order to ensure that acylation is complete (diazotisation and rendering alkaline of the sample no longer gives a red colouration).

Stirring of the mixture is continued for 5 minutes, and 8.7 g of morpholine are then added while maintaining a pH of 7.5 to 8 with 15% strength sodium carbonate solution. After 10 minutes at 10°, the reaction is complete.

The reaction product of the formula ##STR12## has partly precipitated.

A diazo compound obtained in the usual manner by direct diazotisation of 30.3 g of 2-aminonaphthalene-1,5disulphonic acid is added to this suspension at 5° to 10° while simultaneously maintaining the pH at 7.0 to 7.5 by sprinkling in sodium bicarbonate.

After coupling is complete, the dyestuff of the formula ##STR13## λ max=486 nm is salted out, filtered off with suction, dried and milled.

The orange-coloured dyestuff powder is readily soluble in water and dyes cotton by one of the methods customary for reactive dyestuffs in brilliant orange shades (colour indicator number 5).

Further valuable dyestuffs which dye cotton in brilliant orange shades are obtained by repeating the procedure for Example 1, using an equivalent amount of the amines listed below instead of morpholine.

    ______________________________________                                                                           Dye-                                                                           stuff                                                                          λ.sub.max                             Example                                                                               Amine                      (nm)                                         ______________________________________                                          2     Methylamine                486                                           3     Ethylamine                 486                                           4     Dimethylamine              486                                           5     Diethylamine               486                                           6     Isopropylamine                                                           7     Aminoacetic acid                                                         8     Taurine                                                                  9     N-Methyltaurine                                                         10     Methylaminoacetic acid                                                  11     β-Sulphatoethylamine                                               12     β-Sulphatoethyl-β-aminoethyl sulphone                         13     β-Sulphatoethyl-γ-aminopropyl sulphone                       14     β-Methoxyethylamine                                                15     β-Aminopropionic acid                                              16     Methylaminomethanesulphonic acid                                        17     Ethylaminomethanesulphonic acid                                         18     H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                CH.sub.2 OSO.sub.2 H                                                    19     H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.2       20     H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                CH.sub.2 Cl                                                             21     N-Methylbenzylamine                                                     22     1-(β-Aminoethyl)-4-(β-sulphatoethylsulphonyl)-                       benzene)                                                                23                                                                                     ##STR14##                                                              24     Cyclohexylamine                                                         25     Ethanolamine                                                            26     N-Methylethanolamine                                                    27     Diethanolamine                                                          28     3-Methoxypropylamine                                                    ______________________________________                                    

EXAMPLE 29

31.9 g of 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid are dissolved in 400 ml of water under neutral conditions. 300 g of ice are then added, and 8.8 ml of trifluorotriazine are run in while maintaining a pH of 4.0 to 4.5 with 15% strength sodium carbonate solution. Stirring is continued for 5 minutes, and a neutral solution of 17.3 g of m-sulphanilic acid is then added while maintaining a pH of 5.0 to 5.5 with 15% strength sodium carbonate solution. During acylation, the temperature is allowed to rise to 15° to 20°. A diazo compound obtained in the usual manner by diazotisation of 30.3 g of 2-aminonaphthalene-1,5-disulphonic acid is added to the resulting solution of the reaction product of the formula ##STR15## at 5° to 10°, while simultaneously maintaining the pH at 7.0 to 7.5 by sprinkling in sodium bicarbonate. After coupling is complete, the dyestuff of the formula ##STR16## is salted out, filtered off with suction, dried and milled.

The orange-coloured dyestuff powder is readily soluble in water and dyes cotton by one of the methods customary for reactive dyestuffs in brilliant orange shades (colour indicator number 5).

Further valuable dyestuffs which dye cotton in brilliant orange shades are obtained by repeating the procedure for Example 29, using an equivalent amount of the amines listed below instead of m-sulphanilic acid.

    ______________________________________                                                                         Dyestuff                                       Example                                                                               Amine                    λ.sub.max (nm)                          ______________________________________                                         30     Aniline                  488                                            31     N-Ethylaniline           486                                            32     N-Methylaniline          486                                            33     4-Chloroaniline          488                                            34     3-Chloroaniline          488                                            35     2-Chloroaniline                                                         36     o-Toluidine                                                             37     p-Toluidine                                                             38     p-Sulphanilic acid                                                      39     o-Anisidine                                                             40     p-Anisidine                                                             41     4-β-Sulphatoethylsulphonylaniline                                  42     3-β-Sulphatoethylsulphonylaniline                                  43     β-Sulphatoethyl-4-aminobenzyl sulphone                             44     3-Aminobenzoic acid                                                     45     4-Aminobenzoic acid                                                     46     1-Amino-4-methyl-3-β-sulphatoethyl-                                       sulphonylbenzene                                                        47     1-Amino-4-vinylsulphonylbenzene                                         48     1-Amino-3-vinylsulphonylbenzene                                         49     2-Amino-6-β-sulphatoethylsulphonylnaphtha-                                lene-8-sulphonic acid                                                   ______________________________________                                    

EXAMPLE 50

31.9 g of 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid are condensed by the procedure of Example 1 with trifluorotriazine and then with morpholine. A diazo compound obtained in the usual manner by direct diazotisation of 38.3 g of 2-aminonaphthalene-1,5,7-trisulphonic acid is added to the resulting suspension of the monofluorotriazinyl compound at 5° to 10°, while simultaneously maintaining the pH at 7.0 to 7.5 by sprinkling in sodium bicarbonate. After coupling is complete, the dyestuff of the formula ##STR17## is salted out, filtered off with suction, dried and milled.

The orange-coloured dyestuff powder is readily soluble in water and dyes cotton in brilliant orange shades (colour indicator number 5).

If this example is repeated, except that an equivalent amount of the amines mentioned in Example 2 to 28 and 29 to 49 is used instead of morpholine, a pH of 5.0 to 5.5 being maintained for the last-mentioned aromatic amines during condensation with the difluorotriazine compound, this likewise results in reactive dyestuffs which dye cotton in orange (colour indicator number 4).

EXAMPLE 51

31.9 g of 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid are condensed with trifluorotriazine by the procedure of Example 1.5.0 g of ethylenediamine is added to the solution of the resulting difluorotriazine compound at 0° while maintaining a pH of 5.5 to 6.5. After 2 to 3 hours, condensation is complete. A diazo compound obtained in the usual manner by diazotisation of 30.3 g of 2-aminonaphthalene-1,5-disulphonic acid is added to the reaction product of the formula ##STR18## which is largely present as a suspension, while simultaneously maintaining the pH at 7.0 to 7.5 by sprinkling in sodium bicarbonate. After coupling is complete, the dyestuff of the formula ##STR19## which has precipitated as a sparingly soluble compound, is filtered off with suction and stirred again in 1 l of water. 16.9 g of 2,4,6-trifluoro-5-chloropyrimidine are added dropwise at 0° to 5° while maintaining a pH of 7.5 to 8.0 with dilute sodium hydroxide solution. During condensation, the dyestuff goes into solution. After condensation is complete (thin-layer chromatogram), the dyestuff is salted out, filtered off with suction, dried and milled. The orange-coloured powder is readily soluble in water and dyes cotton in clear orange shades (colour indicator number 5).

Further valuable reactive dyestuffs which dye cotton in orange are obtained by repeating this example, using an equivalent amount of the reactive components listed below instead of 2,4,6-trifluoro-5-chloropyrimidine and carrying out the condensation within the temperature range given.

    ______________________________________                                         Example   Reactive component                                                                               Temperature                                        ______________________________________                                         52        4,6-Difluoro-5-chloro-                                                                           10-15°                                                pyrimidine                                                           53        2,4-Dichloro-6-aminotriazine                                                                     25-30°                                      54        2,4-Dichloro-6-(2'-sulpho-                                                                       25-30°                                                phenylamino)-triazine                                                55        2,4-Difluoro-6-(2'-sulpho-                                                                       0-5°                                                  phenylamino)-triazine                                                56        2,4-Difluoro-6-(2'-chloro-5'-                                                                    0-5°                                                  sulphophenylamino)-triazine                                          ______________________________________                                     

I claim:
 1. A reactive dyestuff which, in the form of a free acid, has the following formula ##STR20## in which R is hydrogen or sulpho,A is ##STR21## in which R¹ is hydrogen or C₁ -C₄ -alkyl, which is optionally substituted by OCH₃, OC₂ H₅, COOH, OSO₃ H, SO₃ H, OCH₂ CH₂ SO₂ CH₂ OSO₃ H, OCH₂ CH₂ SO₂ CH═CH₂, OCH₂ CH₂ SO₂ CH₂ CH₂ Cl, SO₂ CH₂ CH₂ OSO₂ H, or SO₂ CH═CH₂, R² is hydrogen, C₁ -C₄ -alkyl which is optionally substituted by OCH₃, OC₂ H₅, COOH, OSO₃ H, SO₃ H, OCH₂ CH₂ SO₂ CH₂ OSO₃ H, OCH₂ CH₂ SO₂ CH═CH₂, OCH₂ CH₂ SO₂ CH₂ CH₂ Cl, SO₂ CH₂ CH₂ OSO₂ H, or SO₂ CH═CH₂, or phenyl which is optionally substituted by Cl, OCH₃, CH₃, SO₃ H, NO₂, COOH, CN, SO₂ CH₂ CH₂ OSO₃ H, SO₂ CH═CH₂, CH₂ SO₂ CH₂ CH₂ OSO₃ H, or CH₂ SO₂ CH═CH₂, or R¹ and R² together form a morpholine ring.
 2. A reactive dyestuff according to claim 1 whereinR¹ is hydrogen or C₁ -C₄ -alkyl, and R² is phenyl which is optionally substituted by Cl, OCH₃, CH₃, SO₃ H, NO₂, COOH, CN, SO₂ CH₂ CH₂ OSO₃ H, SO₂ CH═CH₂, CH₂ SO₂ CH₂ CH₂ OSO₃ H, or CH₂ SO₂ CH═CH₂.
 3. A reactive dyestuff according to claim 1 wherein the dyestuff is of the formula ##STR22##
 4. Process for the dyeing or printing of hydroxyl or amido-containing materials with a reactive dyestuff, by applying thereto a reactive dyestuff according to claim
 1. 